We analysed how citrate (CIT), a chelating agent potentially present in radioactive waste disposals, affects the mobility of four radionuclides (RN): 63Ni, 233U, 152Eu, 238Pu in portlandite, an important hydrated phase of cement, a commonly used material for waste isolation.Portlandite was synthetized in the laboratory and showed high purity and grain size of few μm. This solid, buffers the pH to 12.5 and shows high adsorption capability for the studied RNs: 152Eu and 238Pu exhibited the highest adsorption (Kd ∼1·105 mL g−1) and 233U the lowest (Kd ∼8·102 mL g−1). CIT adsorption was also experimentally evaluated by batch sorption experiments and electrophoretic (ζ-potential) measurements: a non-lineal sorption behaviour was observed, with Kd values decreasing (from ∼1·103 mL g−1) as CIT concentration increased up to 1·10−2 M, according to portlandite sorption sites saturation.In the presence of CIT, a marginal decrease for 233U adsorption in portlandite was observed, one order of magnitude reduction for 63Ni, while 238Pu and 152Eu adsorption decreased significantly. The calculated sorption reduction factors (SRF) for the four RN in the presence of CIT at a concentration of 5·10−3 M were: 2.4, 9.7, 37 and 50.9 for 233U, 63Ni, 238Pu, and 152Eu, respectively.According to the available thermodynamic databases, low complexation between CIT and RN is predicted at pH = 12.5, thus the RN adsorption decrease in the presence of CIT must be attributed to the organic adsorption on portlandite. However, current thermodynamic are still incomplete for this ligand and this pH range and this limits a precise interpretation of the experimental data.